Catalytic polymerization system, their preparation and use

 

(57) Abstract:

The invention relates to catalytic systems, methods for their preparation and their use in the polymerization of olefins. Prepare the catalytic system on a porous carrier by contact with a solution containing the metallocene catalyst component and the activator. The total volume of the solution is in the range of values of the volume, less than three times the single total pore volume of the porous media to a volume greater than a single total pore volume of the carrier. The obtained catalyst system is dried. It is possible that the total volume of the solution was in the range of values of the volume, the smaller the extent that the formed suspension to a volume greater than a single total pore volume of the porous media. It is also possible that spending contacting a porous medium with two or more solutions, one of which includes a metallocene catalyst component, and the other activator. Carry out the polymerization of olefins individually or with one or more olefinic monomers in the presence of this catalytic system on the media. The technical result of the invention consists in the systems, to reduce the clogging of the reactor. 5 C. and 7 C.p. f-crystals, 4 PL.

This patent application is a continuation patent application of U.S. 08/412810 filed March 29, 1995, which is still partially in the application for U.S. patent 08/265533 filed June 24, 1994

THE TECHNICAL FIELD TO WHICH THE INVENTION RELATES

The present invention relates to catalytic systems and methods for their preparation and their use in the polymerization of olefins. The invention in particular relates to a method for the catalytic system on the media for use in gas phase, slurry phase or liquid phase/solution, while improving the operability of the reactor.

BACKGROUND OF THE INVENTION

In many polymerization processes, in particular processes in the suspension phase or in the gas phase, it is advisable to use a catalytic system on the media. Typically, these catalytic systems include metallocene and alumoxane supported on a carrier such as silica. For example, in U.S. patent 4937217 presents a General description of the mixture of trimethylaluminum and triethylaluminum added to neobezjirennogo the silicon dioxide, which then add metal the EPA in the reactor, containing metallocene, trialkylaluminium and diabetogenic silicon dioxide. In U.S. patent 4912075, 4935397 and 4937301 described the addition of trimethylaluminum to neobezjirennogo the silicon dioxide and the subsequent addition of metallocene with getting dry catalytic system on the media. In U.S. patent 4914253 described the addition of trimethylaluminum to neobezjirennogo the silicon dioxide, adding metallocene, followed by drying the resulting catalytic system on the carrier together with a certain amount of hydrogen, resulting in a polyethylene wax. In U.S. patent 5008228, 5086025 and 5147949 describes the preparation of dry catalytic system on the media by the addition of trimethylaluminum in water-soaked silicon dioxide with obtaining in situ alumoxane and by subsequently adding metallocene. In U.S. patent 4808561, 4897455 and 4701432 described methods of preparation of the catalyst on a carrier, in which the inert carrier, typically silicon dioxide, calicivirus and enter into contact with metallocenes (metallocene) and activator-socialisticheskom component. In U.S. patent 5238892 describes the preparation of dry catalytic system on the media mix of metallocene with alkylamines and after the tel metallocen/alumoxane catalytic system by cooking metallocen/alumoxane reaction solution, adding a porous medium and evaporation of the resulting suspension to removal of the carrier residual solvent.

Although all of these catalysts on a carrier suitable for use, however, there is a need for an improved metallocene catalyst system, which upon receipt of the polymers does not contaminate the reactor. Thus, in particular, in the process of polymerization in suspension or in the gas phase with the use of these catalytic systems there is a tendency to the emergence of technological problems in the reactor during polymerization. In a typical polymerization process inside the reactor fines are often accumulates and is glued or sticks to the walls of the reactor. This phenomenon is often called "lacing" or "layering". The accumulation of polymer particles on surfaces/walls of the reactor, recirculation lines, distribution plates, if they are used, and cooling systems raises many issues, including poor heat transfer during the polymerization process. Polymer particles, which stick to the walls of the reactor can continue to cure and often fused, forming clumps that may be able to provide the m there is a need for an improved polymerization catalyst system in the polymerization process substantially improve the efficiency of the reactor and would receive a higher quality of the polymer product.

A BRIEF STATEMENT OF THE SUBSTANCE OF THE INVENTION

The object of the present invention consists of a new catalytic system for the polymerization media, the means of its production and its use in the polymerization process. In one embodiment offers an improved method of obtaining a metallocene catalytic system on the media by introducing a porous medium in contact with a solution comprising metallocene catalyst component and the activator, where the total volume of solution added to the porous carrier is in the range of from not more than is required for the formation of a suspension volume to a volume greater than a single total pore volume of the porous media. Alternatively the porous media is introduced into contact with two or more solutions, one of which includes a metallocene catalyst component, and the other contains an activator, where the total volume of all solutions is in the range snabi pore volume of the porous media.

In other versions of the invention, the total volume of the solution or solutions ["solution(s)"] , added to the porous carrier is in the range of values from three times the total pore volume of the porous media to more than a single total pore volume of the porous media or from 2.5 - to 1.05 times the total pore volume of the porous media, from 2,4 - up to 1.1 times the total pore volume of the porous media, from 2.3 to 1.2 times the total pore volume of the porous media or from 2,2 - up to 1.25 times the total pore volume of the porous media. The resulting catalytic system then dried before use in the polymerization of olefins.

According to another object of the present invention features a method of producing polyolefins of the olefin monomer, optionally with the use of co monomer, in the presence of catalytic systems described above.

According to another object of the invention is proposed catalytic system obtained by the improved method.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The present invention generally relates to a catalytic system on the media, which can be used for polymer clay is Italy metallocene catalyst component or connection in conjunction with the activator or acetalization.

It was found that in the preparation of the catalytic system on the media according to the invention the catalytic activity is retained, and in many cases increases, if the total volume of the metallocene and activator solution is added to the porous carrier is in the range of from not more than is required for the formation of a suspension volume to volume, which exceeds one-time total pore volume of the porous media. The preparation of the catalytic system according to the invention thus results in a simple, suitable for technical use and in terms of value, more efficient catalytic systems on the media with weak tendency to "edging" or clogging the polymerization reactor. In addition, the use of a catalytic system of the present invention provides a polymer product having a high bulk weight with improved physical properties.

The catalytic components of the invention

Metallocene catalyst components generally represent, for example, transition metal compounds with bulky ligand, which can be derived ingredients formula

[L]mM[A]n,

GI n are that the total ligand valency corresponds to the valency of the transition metal. In a preferred embodiment, the catalyst is chetyrehkratnym, so that the connection is able to ionize until the state of charge of 1+.

The ligands L and A may be linked together by a bridge, and in the presence of two ligands L and/or A they can be linked by bridges. These metallocene compounds may be panasoniclumix with compounds containing two or more ligands L, which can be a cyclopentadienyls ligands or ligands that are derived cyclopentadiene, or polyangiaceae compounds comprising one ligand L, which is a cyclopentadienyls ligand or a derivative ligand.

Metallocene compounds contain many related atoms, preferably carbon atoms, and are usually characterized by the presence of a cyclic structure, such as cyclopentadienyls ligand, substituted or unsubstituted, or ligand, which is a derivative of cyclopentadienyl, or any other ligand capable of education-5-connection with the transition metal atom. One or more volumetric liganga metal of group 4, 5 or 6, and/or metal from a number of lanthanides or actinides. With the transition metal can be linked with other ligands, such as tsepliaeva group, for example hydrocarbon, hydrogen or another monovalent anionic ligand, and these examples are not limited. Non-limiting examples of metallocene components and catalyst systems are described, for example, in U.S. patents 4530914, 4952716, 5124418, 4808561, 4897455, 5278119, 5304614, all they are fully included in the present description as a reference. The same applies to European applications 0129368, 0520732, 0420436, international applications 91/04257, 92/00333, 93/08221 and 93/08199, all of which are in full included in this description as a reference.

In the method of polymerization according to the present invention can be used catalytic system metallocene type different forms. Examples of the development of metallocene catalysts in the art for polymerization of ethylene is shown in U.S. patent 4871705, issued in the name Hoel, 4937299, issued in the name of Ewen and others, 5324800 (application for U.S. patent 07/752415, filed on August 30, 1991) and European application 129368, published on July 26, 1989, and U.S. patent 5017714 and 5120867, issued in the name Welborn, Jr., and they are all in full the congestion and enable alumoxane as socializaton. There are different ways of cooking alumoxane, non-limiting examples of which are described in U.S. patents 4665208, 4952540, 5091352, 5206199, 5204419, 4874734, 4924018, 4908463, 4968827, 5308815, 5248801, 5235081, 5157137, 5103031, in the European applications A-0561476, B1-0279586, A-0594218 and in the international application 94/10180, all of which are in full included in this description as a reference.

In addition, the metallocene catalyst component according to the invention can be a containing heteroatom mononitrobenzene connection. This heteroatom activate or alumoxanes, ionizing activator, Lewis acid, or their combination with obtaining the active catalytic system for the polymerization. The catalytic systems of these types are described, for example, in international publication WO 92/00333, 94/07928, 91/04257 and 94/03506, in U.S. patents 5057475, 5096867, 5055438, 5198401, 5227440 and 5264405 and in European patent application A-0420436, all of which are in full included in this description as a reference. Moreover, metallocene catalysts, which can be used according to the present invention may include nasikabatrachidae catalytic components or ancillary ligands, such as broly and Carbolite, in combination with the transition metal. In addition to the identification of the respective products, described in U.S. patent 5064802, 5149819, 5243001, 5239022, 5276208, 5296434, 5321106 and 5304614, international publications WO 93/08221 and 93/08199 and European patent application A-0578838, all of which are included in the present description as a reference.

Preferred transition metals as components of catalytic systems according to the invention are the metals of group 4, in particular zirconium, titanium and hafnium. Such transition metal may be in any oxidation state, preferably +3 or +4, or to be in a mixed state of oxidation. All the catalytic systems according to the invention may not necessarily be prepolymerized or used in combination with additive or removing an impurity component to improve the catalytic performance (see , for example, the publication WO 94/07927 included in the present description by reference).

In the context of this description, the term "metallocene" indicates the contents of one or more unsubstituted or substituted cyclopentadienyl or cyclopentadienyls residues in combination with the transition metal. In one embodiment, metallocene catalyst component corresponds to the General formula (Cp)mMeRnR'pwhere at least the second symmetrically or asymmetrically; Me denotes a transition metal of group 4, 5 or 6; R and R' independently denote halogen, hydrocarbonous group or hydrocarbonbearing group containing 1-20 carbon atoms, or a combination thereof; m is 1-3, n is 0-3 and p denotes 0-3, and the sum of m+n+p equals the oxidation state Me.

In another embodiment, a metallocene catalyst component corresponds to the formula

(C5R'm)pRs(C5R'm)MeQ3-p-xand

Rs(C5R'm)2MeQ',

where Me denotes a transition metal of group 4, 5 or 6, at least one of C5R'mdenotes a substituted cyclopentadienyl, each R', which may be identical or different, denotes hydrogen, alkyl, alkanniny, aryl, alcylaryl or arylalkyl radical containing 1-20 carbon atoms or two carbon atoms connected with the formation of part of a substituted or unsubstituted ring or rings containing 4-20 carbon atoms, R" denotes a radical containing one, several, or a combination of such substituents as atoms of carbon, germanium, silicon, phosphorous and nitrogen, and a connecting bridge two rings (C5R'mor the one ring (C5R'mwith Me, when p is different, denotes aryl, alkyl, alkanniny, alcylaryl or arylalkyl radical containing 1-20 carbon atoms, halogen or alkoxide, Q' denotes alkylidene radical containing 1-20 carbon atoms, s is 0 or 1 and when s is 0, m is 5 and p represents 0, 1 or 2 and when s is 1, m is 4 and p denotes 1.

In the context of this description, the terms "socializaton" and "activators" are used interchangeably, and they refer to any compound or component which can activate the transition metal compound with bulky ligand or metallocene, as described above. The present invention includes the use of alumoxane as activator. There are different ways of cooking alumoxane, non-limiting examples of which are described in U.S. patents 4665208, 4952540, 5091352, 5206199, 5204419, 4874734, 4924018, 4908463, 4968827, 5308815, 5329032, 5248801, 5235081, 5157137 and 5103031, European applications A-0561476, B1-0279586 and A-0594218 and in the international application WO 94/10180, all of which are in full included in this description as a reference. It may be preferable to use a visually transparent methylalumoxane. To obtain a clear solution is turbid or gelatinizing S="ptx2">

The present invention includes, in addition, the use ionizing activators, neutral or ionic, or of compounds such as tri(n-butyl)ammoniates(pentafluorophenyl)boron, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with the remaining ion of the ionizing compound, but not coordinated or only loosely coordinated to it. According to the present invention also provides combinations of activators. For example, combinations alumoxane with ionizing activators are described, in particular, in the international application WO 94/07928.

Descriptions of ionic catalysts for coordination polymerization, comprising metallocene cations contained in such published as European application And 0277003 and 0277004, U.S. patent 5198401 and international application WO 92/00333 (incorporated in the present description by reference). In these publications described the preferred method of receiving, at which metallocene (BISSpand monop) protonium anionic precursor, so that the transition metal is separated alkyl/hydride group, obuslovlena is in coordinational anion" means an anion, which either does not form coordination with the said cation or very weakly coordinated in regard to the said cation being due to it moving enough to replace a neutral Lewis base. "Compatible" recoordination anions are anions that will not destroy to a neutral state when initially decomposes the complex. Moreover, this anion does not transfer an anionic Deputy or fragment to the cation, thereby forming the neutral chetyrekhetazhnoe metallocene compound and a neutral by-product from the anion. Recoordination anions, which can be used in accordance with the present invention, are those that are compatible with the metallocene cation and stabilize it in respect of balancing its ionic charge to the state +1 and yet retain sufficient mobility that it does not interfere with the replacement of the ethylene or acetylene unsaturated monomer during polymerization.

The use of ionizing ionic compounds not containing an active proton but capable of education as an active metallocene cation and sisanie as references)]. In yet another method of obtaining ionic catalysts provided by the use of ionizing anionic precursors, which initially represents a neutral Lewis acid, but the reaction of ionization with metallocene compounds form the cation and anion, for example, using Tris(pentafluorophenyl)boron (see European patent application A-0520732 included in the present description by reference). Ionic catalysts for the polyaddition can be also obtained by the oxidation of the metal centers of transition metal compounds anionic precursors, including along with the anionic groups of the metal-containing oxidizing group (see European patent application A-0495375 included in the present description by reference).

When the metal ligands include haloesters residues (for example, dicyclopentadienyltitanium), which in standard conditions is not capable of ionizing removal, they can be subjected to conversion by known alkylation reactions with metal hydrides or ORGANOMETALLIC compounds such as lithium or aluminiumhydride or alkali, alkylalkoxy, the reagents of Grigna the General description as links), where described reaction aluminiumtechnik connections dialoguescience metallocene compounds prior to or with the addition of activating anionic compounds.

Methods of application on the media of ionic catalysts, including metallocene cations and recoordination anions described in international applications WO 91/09882 and 94/03506 and in co-pending application for U.S. patent 08/248284, filed August 3, 1994 (incorporated in the present description as references). Such methods generally involve either physical absorption by traditional polymer or inorganic carriers which are previously largely dehydration and dehydroxylation, or the use of neutral anionic precursors, which represent a Lewis acid strong enough to activate the held hydroxyl groups in kremnezemsoderzhashchego inorganic oxide carriers, so that the Lewis acid becomes covalently linked, and the hydrogen of the hydroxyl group is available for protonation of metallocene compounds.

In the context of this description, the terms "media" and "substrate" are used interchangeably and can oboronitelnie oxides, inorganic chlorides, in particular magnesium chloride and resinous materials such as polystyrene, polyolefin or polymeric compounds or any other organic material media, etc., the average particle size exceeds 10 μm.

Preferred materials carriers are inorganic oxide materials, which include those consisting of oxides of metals of groups 2, 3, 4, 5, 13 and 14 of the Periodic table of elements. In a preferred embodiment, the carriers for the catalysts are silicon dioxide, aluminum oxide, kranidioti-aluminiumoxid and mixtures thereof. Other inorganic oxides that may be used either individually or in combination with silicon dioxide, aluminum oxide or kremmidiotis-aluminiumoxide include magnesium oxide, titanium dioxide, zirconium dioxide, etc.

In a preferred embodiment, the specific surface area of the carrier for the catalyst of the present invention is from about 10 to about 700 m2/g, its pore volume is from about 0.1 to about 4.0 CC/g and average particle size is from about 10 to about 500 microns. More preferably, the specific surface area costal is the average particle size is from about 20 to about 200 microns. Most preferably, the specific surface area is from about 100 to about 400 m2/g, the porosity is from about 0.8 to about a 3.0 CC/g and average particle size is from about 30 to about 100 microns. Typically, the pore size of the carrier according to the invention is from 10 to 1000, preferably from 50 to about 500 and most preferably 75 to about 350

The method of preparation of the catalytic system according to this invention

There are many different options for preparation of the catalytic system on the media according to the invention.

In the context of this description and the accompanying claims, the term "solution" includes a suspension, a suspension and the mixture. You can use any compatible solvent or other liquid suitable for solution or so on at least one metallocene catalyst component and/or at least one activator. Non-limiting examples of solvents are aliphatic, aromatic and saturated hydrocarbons, and cyclic hydrocarbons such as isopentane, heptane, toluene, etc., the preferred solvents are cyclic aliphatic and aroma of the new catalytic component is suspended in a solvent, getting metallocene solution, and preparing a separate solution containing the activator and a solvent. Then metallocene solution and the activator solution is added to the porous media or Vice versa or in any combination.

In another embodiment, the metallocene solution is added to porous media first, before adding the activator solution. According to another variant of the first activator solution is added to the porous carrier, or Vice versa, and then add metallocene solution. In another embodiment, part or all of the metallocene solution can be added to the porous carrier, or Vice versa, then add all or part of an activator solution. In the case of use of parts of the remaining portion of each of the solutions can be added to the porous carrier in any order.

The carrier preferably be processed containing catalyst(s) component(s) solution so as to obtain a homogeneous catalytic system, i.e. a system in which such an(s) component(s) evenly distributed(s) on the particles of the carrier and inside them. In a preferred embodiment, metallocene catalyst component and the activator are mixed in the solution before rst is imago to the media, is in the range from not more than is required for the formation of a suspension volume to volume, which is approximately equal to the total pore volume of the carrier, preferably the total amount is 2.5 times the total pore volume of the carrier to 1.05 times the total pore volume of the carrier, more preferably from 2.4 times to 1.1 times the total pore volume of the carrier, more preferably from 2.3 times to 1.2 times the total pore volume of the carrier, more preferably from 2.2 times to 1.25 times the total pore volume of the carrier. In a preferred embodiment, the solution is added either dropwise or in aerosol form while mixing media or thoroughly mix in some other way.

Used according to the invention a suspension is formed when one can observe two phases, one of which contains all or most of the media. The volume of solution required to reach this stage, usually varies depending on, among other things, the type of media and type of the components of the catalytic system. The moment of suspension immediately preceding stage, which in this description is defined as "slurry" stage. At this stage slurry solution volume Taco is om. Before the slurry phase volume of the solution is such that in appearance the material of the carrier is in a state of dry and engineering (even though the media may include a solution, the volume of which is close to the single volume of pores) to dry but slightly sticky material of varying degrees of moisture and clumping, which looks like sand with different humidity.

In one embodiment, the volume of solution applied to the carrier is in the range of values from values larger than a single pore volume, to the value, which is necessary for the suspension, preferably from values larger than a single pore volume, to the value that you want to achieve a slurry phase. It should be borne in mind that the catalytic system formed at the slurry stage, it becomes more difficult mixing, and they require a longer drying period in comparison with those prepared with a smaller amount of solution. When less than a single volume of pores achieve uniform coating of the carrier components of the catalytic system can be difficult. This can result in blockage.

Although it does not matter the fact, add thieves to porous media, when the total amount of liquid is less than or equal to a single pore volume of the porous media. In the most preferred embodiment, metallocene and the activator are mixed together to obtain a solution, which is then added to the porous carrier.

Before use in polymerization catalytic system according to the invention is preferably dried at least to the engineering education of the powder. As engineering powder catalytic system according to the invention, however, can contain within the pores of the carrier a certain amount of solvent, for example toluene. Another variant of this catalytic system can be dried in such a way as to remove from it almost all the solvent. In the context of this description and the accompanying claims the term "remove almost all solvent" means that during the drying of the catalytic system on the media out of it removed about 90% of the total solvent.

In another embodiment, the dried catalytic system on the media is washed or treated in any other way to remove loosely associated with the catalytic component(s). For washing the catalytic system can be used in the element and should be easily removed from the carrier during drying. The preferred toluene and hexane.

The present invention also includes individual applying at least one metallocene one porous carrier and applying at least one activator on the other porous media, where the total volume of the metallocene solution on the first porous medium and the total amount of an activator solution described above.

Methodology to measure the total volume of pores of porous media are well known in the art. Detail one of such methods is described in Experimental Methods in Catalytic Research (Academic Press, 1968), 1 so, (especially see pp. 67-96). This preferred method provides for the application of the classical BET unit for absorption of nitrogen. Another method well known in the art, described by Innes in Total Porosity and Particle Density of Fluid Catalyst by Liquid Titration, T. 28, 3, Analytical Chemistry 332-334 (March, 1956).

In another embodiment, the molar ratio between the metal of the activator component and the transition metal metallocene component is from 0.3:1 to 1000:1, preferably from 20:1 to 800:1 and most preferably from 50:1 to 500:1.

In another embodiment, in which the activator is an ionizing activator, which describes the screens from 0.3:1 to 3:1.

In yet another embodiment, a catalytic system on the media according to the invention includes a polyolefin wax, a substance for increasing the adhesiveness or etc.

The method of polymerization according to the invention

The catalytic system of the present invention is suitable for polymerization of the monomers and optional comonomers in any polymerization process or prepolymerisation in the gas, slurry or solution phase. You can even use the process is conducted under high pressure in an autoclave. In the preferred embodiment, is applied t the process in the gas phase or in suspension phase, the most preferred gas-phase process.

In a preferred embodiment, the present invention relates to suspension and gas-phase reactions of polymerization and copolymerization, including polymerization or the optional prepolymerisation one or more alpha-olefin monomers containing from 2 to 20, preferably 2-12 carbon atoms. The present invention is particularly suitable for copolymerization reactions involving the polymerization of one or more monomers, for example alpha-olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, the monomers, diolefin, such as diene, norbornene, norbornadiene, acetylene and aldehyde monomers. It is preferable to obtain a copolymer of ethylene or propylene. The preferred co monomer is an alpha olefin containing from 3 to 15, preferably 4 to 12 and most preferably 4-10 carbon atoms. In another embodiment, the ethylene or propylene will polimerizuet together at least two comonomers with obtaining ternary copolymer, etc.

In one embodiment of the method according to the invention prior to the main polymerization of olefin(s) will prepolymerized in the presence of a catalytic system according to the invention. This prepolymerisation can be conducted intermittently or continuously in the gas, solution or slurry phase, including the application of high pressure. Prepolymerisation can be performed using any alpha-olefin monomer, or combinations and/or in the presence of any agent of regulating the molecular weight, such as hydrogen. In more detail prepolymerisation described, for example, in U.S. patents 4923833 and 4921825 and in European application-0279863, published on 14 October 1992, all in full included in this description as a reference. To improve the catalytic PR is used in combination with additive or impurity binding component.

As a rule, in the process of gas-phase polymerization apply a continuous cycle in which part of the circulating mass reactor, the circulating gas stream, otherwise known as a recycle stream or pseudozyma environment, is heated in the reactor by the heat of polymerization. This heat away in another part of the cycle with a cooling system outside the reactor (see, for example, U.S. patents 4543399, 4588790, 5028670 and 5352749 and international application WO 94/28032, published on 8 December 1994, all of which are in full included in this description as a reference).

Usually in the case of fluidized gas layer in the process of obtaining a polymer from monomers of the gaseous flow comprising one or more monomers in the presence of catalyst under reaction conditions continuously passed through a fluidized bed. This gaseous stream is removed from the fluidized bed and return to the reactor. At the same time from the reactor to remove the polymer product and to replace the polymerized monomer or add a new fresh monomer.

The process of suspension polymerization is usually carried out under pressure in the range of from about 1 to about 500 atmospheres or even higher and at a temperature in the range of ovat in a liquid polymerization medium, to which is added ethylene and comonomers and often hydrogen together with the catalyst. As the liquid used in the polymerization environment, you can use alkane, cycloalkane or aromatic hydrocarbon, such as toluene, isobutylene, ethylbenzene or xylene. The polymerization conditions used, the environment must be in a liquid state and to be relatively inert. It is preferable to use hexane or isobutane.

Polymer composition and scope of the invention

DFID or the polydispersity is a well-known characterization of polymers. DFID is typically represented as a ratio between srednevekovoi molecular weight (Mwand srednekamennogo molecular weight (Mn). The ratio of Mw/Mncan be defined directly using the method gel chromatography or indirectly by determining the ratio between the I21and I2as specified in the standards accordingly to ASTM D-1238-F and ASTM D - 1238-that is, In this technical field parameter I2well known as the equivalent melt index (IL). I21also known as the melt index under a heavy load (IRBN). The value of IL is inversely proportional to moleculesin, preferably from about 0.2 to about 300 DG/min, more preferably from about 0.3 to about 200 DG/min and most preferably from about 0.5 to about 100 DG/min

The ratio of I21/I2it is known as the ratio of the melt index (SIR), and in the context of this description, this ratio is also defined as the ratio of the melt viscosities (SVR). In General, the value of SIR is proportional to MMD.

CYR for polymers of the present invention is usually from more than 10 to about 200, preferably from about 12 to 60 and most preferably from about 14 to about 45.

Density ethylene homopolymer and copolymer compositions according to the invention is from about 0,86 to about 0.97 g/cm3preferably from approximately 0.88 to about 0.96 g/cm3more preferably from about 0.90 to about 0,955 g/cm3and most preferably from about 0.91 and about 0.95 g/cm3.

DFID polymers according to the invention is more than about 1.8 to less than about 20, preferably in the range from more than about 2 to about 5.

Another important characteristic of the polymer according to the invention is its distribution is. PSRS defined as the weight percentage of copolymer molecules, content comonomeric links which is within 50% (i.e. 25% on each side) from the average total molar content comonomeric links. PSRS copolymer can be easily identified using well known methods for the selection of individual fractions of the sample of the copolymer. One of such methods is the method of elution fractions with increasing temperature (EFPT), as described by Wild and al. in J. Poly. Sci., Poly. Phys. Ed., volume 20, page 441 (1982), and in U.S. patent 5008204, which are included in the present description as a reference.

To determine PSRS first copolymer build distribution curve of solubility. This can be performed using the data obtained from the above-described methods APPT. This distribution curve of solubility is a graph of the weights solubilizing copolymer of temperature. It is converted into a curve according to the weight percentage distribution of the composition. In order to simplify the correlation structure on the temperature of the elution value of Mnthe weight fractions accept 15000, where Mndenotes the share of srednekamennogo molecular weight. Small weights prilagaemyi claims confirm validity of the adoption of this condition about when determining PSRS all weight fractions are characterized by Mn15000.

Along the curve according to the weight percentage distribution by composition PSRS determined by establishing what the weight percentage of the sample has a content comonomeric links within 25% of each side of the average amount of monomer units. Other details of the definition PSRS copolymer known to experts in the art (see, for example, application WO 93/03093, published on February 18, 1993).

In one embodiment, PSRS polymers of the present invention typically ranges from over 50% to 99%, preferably from 50 to 85%, more preferably from 55 to 80%, even more preferably greater than 60% and most preferably greater than 65%. Obviously, with other catalytic systems and by making changes in the process conditions can be achieved a higher or lower values PSRS.

In some cases, when it is necessary to improve processability and to make changes in operational characteristics of the finished product, the polymers obtained according to the present invention, it is possible to mix and work together to ekstradiroval with a molded one - ili equipment, as, for example, LLDPE, LDPE, polyethylene high and low density, polypropylene, PB, EMA, EVA, copolymers of acrylic acid, polymethylacrylate and any other polymers, such as polyvinylchloride, polybutene-1, isotactic polybutene, ABS - plastics, ethylene-propylene rubber, vulcanized ethylene-propylene rubber, EPDM block-copolymer elastomers, copolymers of ethylene with vinyl alcohol, polystyrene, nylon, PET resins, crosslinked polyethylene, poly-1 esters, grafted copolymers, polyacrylonitrile homopolymers or copolymers, thermoplastic polyamides, Polyacetal, polyvinylidene fluoride and other fluorinated elastomers, polyethylene glycols, polyisobutylene, terpene resins and other polymers, giving a viscous polymers, etc., and combinations thereof.

In many applications the polymer according to the invention it is expedient to combine with antioxidant agent, giving a slip agent, prevent caking, substances to improve the processing properties, pigments, inhibitors that protect from UV rays, antistatic agents or other additives. The polymers obtained by the method according to the invention can be used in the process of forming akem, molding and centrifugal casting. The films are materials, molded blown, and irrigation in the form of single layer and multilayer structures produced by coextruding or lamination. Such films can be used as shrink films, adhesive tapes, stretch film, sealing films for seals, oriented films, packaging for food, durable bags for heavy cargo, packages for groceries, packaging for baked and frozen food packaging supplies, industrial linings, membranes, etc. in those applications where they are in contact and not in contact with food products. The process of forming fibers include spinning from melt spinning from solution and blow molding fibers from the melt. Such fibers can be used in the form of woven and nonwoven materials for the manufacture of filters in the form of salfetochnyj of textiles, clothing, health care workers, geotextile materials, and the like. To conventional extruded products include tubes for medical purposes, coatings for wires and cables, geomembranes and facing materials for swimming pools. Molded products include single - and many who Isaevich products toys, etc.

EXAMPLES

The following examples serve to clarify the essence of the present invention, including its characteristic advantages and its limits.

The density was measured in accordance with ASTM D-1238. The ratio of Mw/Mncan be measured directly using gel chromatography. According to this description, DFID polymer was determined using chromatograph Waters Gel Permeation Chromatograph equipped with speakers with gel Ultrastyrogel and detector refractive index. In this configuration, the operating temperature in the apparatus was maintained at a level 145oC, as a solvent for elution used trichlorobenzene, and the calibration standards included sixteen polistirolo precisely known molecular weight, which ranged from 500 to 5.2 million, and plastic NBS standard 1275. In all examples as the material of the upper layer solution was used methylalumoxane in toluene concentration of 30 wt.%, which comes to the market company Ethyl Corporation, Baton Rouge, PCs Louisiana, and which in the art otherwise known as transparent methylalumoxane.

Example 1

Method 1

Alumoxane in toluene is mixed with metallocene logicheskie add to it a solution of the precursor. Between stages added, the vessel is tightly closed and the mixture of silicon dioxide from the precursor mix by intensive shaking. The total amount of added precursor does not exceed the total available pore volume of the silica, and the mixture always consists of finely ground engineering particles. In this way, the precursor is uniformly injected into the pores of the silica. Toluene can be removed in a vacuum to prevent further weight loss.

The catalyst 1-1

The precursor is prepared by stirring the mixture to 19.61 g of the solution methylalumoxane in toluene concentration of 30 wt.% (82,37 mmole A1) and 0,548 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (1,27 mmole Zr). In accordance with method 1 2,04 g of precursor added to 2,182 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 0.63. Fine engineering solid material is dried under reduced pressure (in vacuo 28+ inches of RT. Art.) and at 40oC for 4 h in This way get 3,10 g of catalyst. Elementary anei stirring the mixture 30,27 g of the solution methylalumoxane in toluene concentration of 30 wt.% (127,13 mmole Al) and 0,556 g of bis(1-butyl-3 - methylcyclopentadienyl)zirconiated (1,29 mmole Zr). In accordance with method 1 4,205 g of precursor added to 2,982 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 0.95. Fine engineering solid material is dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40oC for 4 h Elemental analysis showed the presence of 0.39 wt.% Zr and 12,93% wt. A1.

The catalyst 1-3

The precursor is prepared by stirring a mixture of 7.25 g of the solution alumoxane in toluene concentration of 30 wt.% (0,037 mol) with 1.09 g of toluene and 0,153 g of bis(1-butyl-3 - methylcyclopentadienyl)zirconiated (0.35 mmole). In accordance with method 1, this precursor is added to 6,004 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is of 0.91. The solid material is completely engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 h

The catalyst 1-4

The precursor is prepared at peremeshivaniem)zirconiated (0.35 mmole), but without the addition of toluene. In accordance with method 1, this precursor is added to 6,002 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica 0.79. The solid material is completely engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 h

Example 2

Method 2

Alumoxane in toluene is mixed with metallocenes with obtaining a solution of the precursor. Silicon dioxide is loaded into a vessel equipped with a stirrer made of many wire loops. This agitator rotates and passes through the entire volume of the vessel. Added dropwise a solution of the precursor. The total amount of added precursor does not exceed the total pore volume of the silica and the mixture is composed of finely ground engineering particles. In this way, the precursor is uniformly injected into the pores of the silica. The toluene is removed in a vacuum to prevent further weight loss.

Catalysts 2-1 and 2-2

The solution of the precursor is prepared by stirring a mixture of 130,0 g of the solution methylalumoxane the La Zr). In accordance with method 2, the precursor is added to 150 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 0.60. About one third of this fine engineering of the catalyst is dried under reduced pressure (vacuum 25,4 inch RT.CT.) and if 25oC for 16 h in This way obtain 93 g of catalyst. Elemental analysis showed the presence of 0.5 weight. % Zr and 9,65% wt. Al. The remaining two-thirds of finely engineering add catalyst precursor containing 48,35 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,249 mole of Al) and 1.65 g of bis(1 - butyl-3-methylcyclopentadienyl)zirconiated (3,81 mmole Zr). The value of the ratio between the liquid volume and the total pore volume of the silica is 0,88. Fine engineering solid material is dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and if 25oC for 16 h in This way obtain 183 g of catalyst. Elemental analysis showed the presence of 0.7 wt.% Zr and 13,03% wt. Al.

Example 3

Method 3

Alumoxane in toluene is mixed with Metalli, adapted for high speed rotation. Added dropwise a solution of the precursor. The total amount of added precursor does not exceed the total available pore volume of the silica and the mixture is composed of finely ground engineering particles. In this way, the precursor is uniformly injected into the pores of the silica. The toluene is removed in a vacuum to prevent further weight loss.

Catalysts 3-1 and 3-2

The solution of the precursor is prepared by stirring a mixture of 77,16 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,397 mole of Al) and 1.56 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (3,61 mmole Zr). In accordance with method 3 precursor add to 59,92 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 0,88. About half of this fine engineering of solid material is dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and at 85oC for 4 h in This way get 40,31 g of catalyst. Elemental analysis showed the presence of 0.37 wt.% Zr and 11,83% wt. Al. The remaining thinoC for 16 h, getting 183 g of catalyst. Elemental analysis showed the presence of 0.35 wt.% Zr and 11,02% wt. Al.

The catalyst 3-3

With the use of the vessel for the preparation of the catalyst described in method 3, 6,48 g of the solution methylalumoxane in toluene concentration of 30 wt.% (33,41 mmole Al) add to 10,217 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 0.43. Then add a solution 0,264 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (0,61 mmole Zr) 4,27 g of toluene. Next add 6.50 g of a solution methylalumoxane in toluene concentration of 30 wt.% (33,51 mmole Al). During the last stage added to remove excess toluene and conservation values of the ratio between the liquid volume and the total pore volume of the silica at a level of approximately 1 use the purge weak current2. Fine engineering solid material is dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40oC for 4 h in This way get 18,73 g of catalyst. Elemental analysis showed the presence of 0.33 wt.% Zr and 11,75% wt. Al.

oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is of 0.44. After that add another 9,78 g of the solution methylalumoxane in toluene concentration of 30 wt.%. The value of the ratio between the liquid volume and the total pore volume of the silica is 0,88. Fine engineering solid material is dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40oC for 4 h in This way get 25,46 g of catalyst. Elemental analysis showed the presence of 0.35 wt.% Zr and 11,37% wt. Al.

Example 4

Method 4

Similar to method 2 alumoxane in toluene is mixed with metallocenes with obtaining a solution of the precursor. Silicon dioxide is loaded into a vessel equipped with a stirrer made of many wire loops. This agitator rotates and passes through the entire volume of the vessel. Silicon dioxide is rapidly added to a solution of precursor or Vice versa. The total amount of added precursor exceeds the total available volume to prevent further weight loss.

The catalyst 4-1

The precursor is prepared by stirring a mixture of 325 ml methylalumoxane in toluene concentration of 30 wt.% (1,56 mol) with 358 g of toluene and 6.5 g of bis(1-butyl-3 - methylcyclopentadienyl)zirconiated (0,015 mol). In accordance with method 4 in this predecessor add 250 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 850oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.8. The solid material is neither gelatinization nor fully engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for two 16-hour periods.

Example 5

Method 5

Alumoxane or suitable activator, such as B(C6F5)3in toluene is mixed with metallocene getting the solution predecessor. In a glass vessel loaded silicon dioxide and add one portion of the entire solution predecessor. Another option in a glass vessel load solution predecessor to this precursor add one portion of the entire silicon dioxide. Mix with a spatula mix thoroughly. The total amount of predshestvenniki gelatinization or mist. The toluene is removed in a vacuum to prevent further weight loss.

The catalyst 5-1

The precursor is prepared by stirring a mixture of 36,27 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,184 mol) with 42.8 g of toluene and 0,781 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (1,81 mmole). In accordance with method 5 in this predecessor add 30,01 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.8. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for two 16-hour periods.

Catalyst 5-1A

The precursor is prepared by stirring a mixture of 36,27 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,184 mol) with 118 g of toluene and 0,783 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (1,81 mmole). Then this predecessor while stirring with a magnetic bar stirrer add 30,01 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), pre naked the silicon is 3.7. Suspension is dried with stirring under reduced pressure (28+ inches of RT.CT.) until then, until it becomes engineering solid material, after which the stirring is stopped and the drying continued at 25oC for 16 hours.

The catalyst 5-2

The precursor is prepared by stirring a mixture of 0,205 g of the solution B(C6F5)3in toluene (0,400 mmole) of 14.2 g of toluene and 0,144 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (of 0.333 mmole). In accordance with method 5 this precursor is added to 6,01 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.3. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 hours.

Catalysts 5-3, 5-4 and 5-5

The precursor is prepared by mixing depreciation is 29.06 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,148 mol) ratio of 36.9 g of toluene. In accordance with method 5 this precursor is added to 24,36 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), previously the IDA silicon is 1.5. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 hours. The obtained solid material was stirred with 300 ml of pentane and filtered. The solids are washed with 100-ml, four 250-ml portions of pentane, and then dried under reduced pressure (28+ inches of RT.CT.) and if 25oC until reaching constant weight.

Next, the second precursor is prepared by mixing 0,094 g of bis(1-butyl-3 - methylcyclopentadienyl)zirconiated (0,217 mmole) from 10.98 g of toluene. This precursor is added to 5,001 grams of dried mixture methylalumoxane/silicon dioxide, the resulting mixture was mixed thoroughly with a spatula and dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 hours.

The third precursor is prepared by mixing to 0.060 g dimethylsilane (tetramethylcyclopentadienyl) (adamantylamine)titjikala (0,134 mmole) with 5.8 g of pentane and 2 g of toluene, heated to 40oC. This precursor is added to 3,012 g of the dried mixture methylalumoxane/silicon dioxide or compounds, the resulting mixture was mixed thoroughly with a spatula and dried under reduced pressure (28+ inches of RT.V. the reattaching the 0,031 g dimethylsilane(tetramethylcyclopentadienyl) (adamantylamine)titjikala (0,069 mmole) and to 0.055 g of bis(1 - butyl-3-methylcyclopentadienyl)zirconiated (to 0.127 mmole) with 3.5 g of pentane and 1.7 g of toluene, heated to 40oC. This precursor is added to 3,000 g of the dried mixture methylalumoxane/silicon dioxide, the resulting mixture was mixed thoroughly with a spatula and dried under reduced pressure (28 + inches of RT.CT.) and if 25oC until reaching constant weight.

The catalyst 5-6

The precursor is prepared by stirring a mixture of 7,434 g of the solution methylalumoxane in toluene concentration of 30 wt.% (of 37.7 mmole) of 9.21 g of toluene and 0,601 g dimethylsilane(tetramethylcyclopentadienyl) (tert-butylimido)dimethylsilane (1,37 mmole). In accordance with method 5 in this predecessor add 5,994 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.1. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for two 16-hour periods.

The catalyst 5-7

The precursor is prepared by stirring a mixture of 36,27 g of the solution alumoxane in toluene concentration of 30 wt.% (0,184 mol) with 42.8 g of toluene and 0,781 g of bis(1-butyl-3-methylcyclopentadienyl)Zirconia stost of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.8. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT. Art.) and at 25oC for 16 h

The catalyst 5-8

The precursor is prepared by stirring a mixture of 7.25 g of the solution alumoxane in toluene concentration of 30 wt.% (0,037 mole) 4.75 g of toluene and 0.152 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (0.35 mmole). In accordance with method 5 in this predecessor add 6,009 g of silicon dioxide (MS948, the porosity of 1.6 CC/ g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica is 1.3. The solid material is neither a suspension nor a fully-engineering; it is dried under reduced pressure (28+ inches of RT.CT.) and if 25oC for 16 h

Example 6

Method 6

Alumoxane or suitable activator, such as B(C6F5)3in toluene is mixed with metallocene getting the solution predecessor. In a glass vessel while caution is destroying silicon dioxide and add a solution of the precursor. Another option in a glass vessel with stirring download solution predecessor to this predecessor to add silicon dioxide. The initial volume of the precursor exceeds the total available pore volume, but not more than double this total available pore volume, so that the mixture does not contain free flowing solvent and does not reach a state of suspension. Add a further portion of the solvent, the volume of which is less than the total pore volume, and stirring is continued. The toluene is removed in a vacuum to prevent further weight loss.

The catalyst 6-1

The precursor is prepared by stirring a mixture of 36,27 g of the solution methylalumoxane in toluene concentration of 30 wt.% (0,187 mol) with 42.2 g of toluene and 0,781 g of bis(1-butyl-3-methylcyclopentadienyl)zirconiated (1,81 mmole). In accordance with method 6 in this predecessor type of 30.00 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co. ) previously heated to 800oC current N2and mix. The mixture was added additionally to 20.9 g of toluene and stirring is continued using a magnetic bar stirrer. The initial value of the ratio between the liquid volume and the total amount the p silicon dioxide is 2.1. The mixture was kept at 80oC for four hours and dried with stirring under reduced pressure (28+ inches of RT.CT.) until then, until it becomes engineering solid material, after which the stirring is stopped and the drying continued at 25oC for 16 hours.

THE POLYMERIZATION TEST OF CATALYSTS

As described below to study the copolymerization of ethylene with 1-hexene used samples of the catalysts according to the invention, which are prepared by the method described above as catalysts 2-1,3-1,3-2,4-1, 5-1, 5-1A and 6-1. Used gas-phase reactor of continuous fluidized bed, working under the total pressure of 300 pounds per square inch. Into the reactor was introduced a solution TEAL in isopentane concentration of 1 wt.%. Table 1 details the composition of the obtained ethylene-1-hexenoic composition together with the process data. Upon completion of a few turns of a layer samples of the polymers were collected and analyzed.

Polymerization catalysts 1-1, 1-2, 2-2, 3-3 and 3-4

Catalysts 1-1, 1-2, 2-2, 3-3 and 3-4 were experienced in the process of suspension polymerization in hexane as follows.

A 2-liter reactor was loaded with 800 ml of hexane which was gregali 0,125 g of each of the catalysts together with ethylene, amount which would have been sufficient to increase the total excess pressure in the reactor to 150 psig (1136 kPa). Within 40 min was introduced ethylene, and then the flow was stopped. The reactor was cooled and the pressure is discharged through the ventilation device. A suspension of polyethylene in hexane from the reactor was removed and the hexane was allowed to evaporate. The remains of the volatile substances were removed at the 75oC in vacuum. Powdered polyethylene (PE) were weighed. The obtained data are presented in table 2.

Polymerization catalysts 5-2, 5-3, 5-4, 5-5 and 5-6

Polymerization was performed in 400 ml of dry hexane in a stream of nitrogen which was passed through a 1-liter Zipperclave reactor (firm Autoclave Engineers) equipped with an external jacket for temperature control. In the glove chamber portion of the catalyst on the carrier, typically 50-200 mg, was administered in a short tube of stainless steel between two ball valves, connected with a small pressure vessel containing 20 ml of dry hexane. This device was connected to the reactor purged with nitrogen. Into the reactor were introduced 0,200 ml of triethylaluminum as socializaton in heptane concentration of 25 weight. % and 45 ml of dry 1-hexene and the mixture with stirring, was heated on the pressure of compressed ethylene 75 pounds per square inch (517 kPa). Immediately after that, stirring was resumed, while due to the ethylene pressure in the reactor reached its regulated operating level 75 psig (517 kPa) (plus the vapor pressure of the solvent). After 30 min the pressure in the reactor was discharged through the ventilation device, the content was poured into chemical glass in the air and filtered. The obtained data are presented in table 3.

Polymerization catalysts 1-3, 1-4, 5-7 and 5-8

Polymerization using catalysts 1-3, 1-4, 5-7 and 5-8 were carried out in accordance with the method described for experiments, data are presented in table 3. The results of these latter experiments are presented in table 4. The use of catalysts in which the volume of solution precursor was found to be less than the total volume of the pores of the support, has resulted in contamination of the walls of the reactor and the agitator.

Although the present invention is described and illustrated with reference to specific ways of its implementation, for any expert in the art it is obvious that the invention can make various changes, which need not be illustrated in this description. So, for example, about the or the use of the catalyst according to the invention together with another catalyst or catalytic system, known in the art, for example with a conventional catalyst or catalytic system of the Ziegler-Natta. In addition, the catalytic system according to the invention can be used in a single reactor or in a series of reactors installed in series. Thus, the scope of the present invention is defined only by the attached claims.

1. The method of preparation of the catalytic system on the media, including the media, the metallocene catalyst component and the activator, by contacting a porous support with a solution containing the metallocene catalyst component and the activator, characterized in that the total volume of the solution containing the metallocene catalyst component and the activator is in the range of values of the volume, less than three times the total pore volume of the porous media to a volume greater than a single total pore volume of the porous media, and the resulting contact of the catalytic system is subjected to drying.

2. The method according to p. 1, where the solution includes dimethylsilane(tetramethylcyclopentadienyl)(adamantylamine)tiandihui.

3. The method of preparation of the catalytic cysteine porous carrier with a solution, containing metallocene catalyst component and the activator, characterized in that the total volume of the solution containing the metallocene catalyst component and the activator is in the range of values of the volume, the smaller the extent that the formed suspension to a volume greater than a single total pore volume of the porous media, and the resulting contact of the catalytic system is subjected to drying.

4. The method according to p. 1 or 3, characterized in. what is the total volume of the solution is in the range of values of the volume, the smaller the extent that the formed suspension to a volume greater than a single total pore volume of the porous media.

5. The method of preparation of the catalytic system on the media, including the media, the metallocene catalyst component and the activator, by contacting a porous support with a metallocene catalyst component and the activator, characterized in that the conducting contacting a porous medium with two or more solutions, one of which includes a metallocene catalyst component, and the other includes an activator, where the total volume of the solution is in the range of values of the volume, aristovo media.

6. The method according to PP. 1, 3 and 4, characterized in that the total volume of solution (s) is 2.5 times the total pore volume of the porous media to 1.05 times the total pore volume of the porous media.

7. The method according to PP.1, 3-6, characterized in that the total volume of solution(s) is from 2.4 times the total pore volume of the porous media to 1.1 times the total pore volume of the porous media.

8. The method according to PP.1, 3-7, characterized in that the solution comprises one or more than one, e.g. two, metallocene catalyst component and one or more than one, e.g. two, of the activator.

9. The method according to PP.l, 3-8, characterized in that before coming in contact with the solution(s) a porous carrier dehydrate.

10. The method according to PP. 1, 3-9, characterized in that the molar ratio between the metal of the activator and a transition metal metallocene catalyst component is from 20:1 to 800:1.

11. The method of polymerization of olefin individually or in combination with one or more other olefin monomers, comprising polymerization in the presence of catalytic systems on the media containing media, the metallocene catalyst component and the activator, characterized t

12. The catalytic system on the media containing the medium metallocene catalyst component and the activator, characterized in that it is obtained by the method according to any of paragraphs.1, 3-10.

Priority points:

24.06.94 on PP.1-12;

29.03.95 on PP.1-12.

 

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